JPH103003A - Production of color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a color filter having a small level difference between pixels and no bubble. SOLUTION: In this method for manufacturing color filter, a multicolor pattern is formed by repeating processes containing (1) a sticking process in which a photosensitive film having a base film and a colored photosensitive resin layer is stuck on a transparent substrate so that the colored photosensitive resin layer is faced to the substrate, (2) an exposing process in which the photosensitive film is exposed in pattern shape and (3) a developing process. In this case, at the process for a secondary or succeeding coloring, a process in which the substrate on which the colored photosensitive resin layer is stuck is cooled to prevent generation of bubbles is included after the (1) process.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a color filter.

[0002]

2. Description of the Related Art A color filter is formed by forming two or more kinds of very fine stripe-like or mosaic-like patterns having different hues on a surface of an optically transparent substrate such as glass in parallel or intersecting at regular intervals. It is a thing arranged. 2. Description of the Related Art There is known a method of manufacturing a color filter that can easily form a multicolor fine stripe or mosaic pattern with high accuracy using a base film and a photosensitive film having a photosensitive resin layer.

[0003] As a method of producing a color filter using a photosensitive film, a photosensitive resin composition colored in one color is applied to a base film and dried, and the photosensitive resin layer of the photosensitive film is coated on a transparent substrate. (See Japanese Patent Application Laid-Open Nos. 61-99102 and 3-1).
JP 60454, JP-A-3-111802, JP-A-2-151805, JP-A-4-212161
JP, JP-A-4-301602, JP-A-5-2
No. 107 publication) is known. In the conventional color filter manufacturing method, when forming the second and subsequent color layers, bubbles are formed between the second and subsequent color layers on the already formed colored layer and the colored layer directly in contact with the substrate. Occurs. These bubbles exceed 10.0 μm at the maximum and cannot be put to practical use. When bubbles are generated, the surface of the three-color pixels becomes uneven, and desired pixels cannot be obtained, resulting in image defects and color unevenness. After heating the substrate, it is not possible to improve the generation of bubbles only by adhering the colored photosensitive resin layer to the substrate and removing the protective film of the photosensitive film by passing it through a pressure roll (lamination).

[0004]

An object of the present invention is to provide a method of manufacturing a color filter having a small step between pixels and having no bubbles.

[0005]

According to the present invention, there is provided a photosensitive film having a base film and a colored photosensitive resin layer on a transparent substrate. (1) A colored photosensitive resin layer is provided on a surface of the substrate. In a method for manufacturing a color filter in which a multicolor pattern is formed by repeating a step of laminating to form a multicolor pattern by repeating a step including (2) an exposing step of exposing in a pattern and (3) a developing step, 1)
After the step, the method includes a step of cooling the substrate to which the colored photosensitive resin layer is attached to prevent generation of bubbles, and a method for manufacturing a color filter.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS By performing a step of cooling the substrate after the step of laminating to prevent the generation of bubbles, it becomes possible to manufacture a color filter comprising excellent pixels without bubbles. After heating the substrate, the protective film of the photosensitive film is peeled off and the colored photosensitive resin layer is adhered to the substrate and passed through a pressure roll (lamination) to prevent the generation of bubbles. In the present invention, the term "bubble" means that there is no colored photosensitive resin layer between the base film and the substrate when the colored photosensitive resin layer is in close contact with the filter substrate having the preceding pixel without any gap. First, the operation principle of the generation of bubbles will be described, and the operation of the solution (the method for manufacturing the color filter of the present invention) will be described.

Description of the principle of operation in which bubbles are generated Under normal laminating conditions (roll temperature, laminating speed, substrate temperature), when the colored photosensitive resin layer has a film thickness of about 2 μm, bubbles in the second and subsequent colors are 4 to 10 μm. Appearing in the size of. The principle of operation in which this bubble is generated is as follows. For example, a case of a single-layer film comprising a 6 μm polyethylene terephthalate film (PET) as a base film and a 2 μm photosensitive layer will be described below.

(A) Under normal laminating conditions, the photosensitive layer
Adhere to 100% substrate glass. PET by roll pressure
Transforms. Deformation consists of elastic deformation and plastic (creep) deformation. Elastic deformation consists of two components, a dynamic elastic force that recovers immediately and a relaxed elastic force that recovers gradually.

(B) After the roll pressure is released, the PET contracts and deforms due to the dynamic elastic deformation that recovers immediately. This is a springback phenomenon well known in so-called press working and the like. Springback refers to a phenomenon in which when a bent product is removed from a mold, the deformation is slightly elastically restored and the same thing as the mold cannot be obtained. This is a fundamental phenomenon in all materials and is one of the fundamentals of material mechanics. When the base film is pressed and extended by a roll and deformed, the same phenomenon occurs in the base film, and the base film shrinks and deforms. This is the source of the occurrence of a step in the pixel. Since the photosensitive layer is melted and flown, the phenomenon of springback is small. The photosensitive layer comes off the PET and adheres to the glass. At this time, a space appears between the contracted and deformed PET and the photosensitive layer, which causes various inconveniences. When this space is generated, the photosensitive layer is melted and flowed, and is simultaneously deformed by an external force. Since the deformation is not uniform and the photosensitive layer melts and flows easily due to the high temperature, bubbles are generated. The generation of bubbles is remarkable in the photosensitive layer portion which is in contact with a substance having a different surface tension, such as a foreign substance, a stain on the substrate surface, or a lubricant on the PET surface, and which is easily melted and flows.

(C) After releasing the roll pressure, the PET contracts and deforms due to the gradual elastic deformation of the recovery. P over time
ET shrinks and deforms (peeling of PET) increases. Also at this time, since the photosensitive layer is easily melted and flows due to the high temperature, bubbles are generated. The space between the PET and the photosensitive layer that contracted and deformed with the passage of time became larger, and air bubbles were more likely to be generated. In the process from (a) to (c),
Bubbles are generated.

The operation principle of generating bubbles has been described above. The operation and effect of the present invention are as follows. The fact that the generation of bubbles can be reduced by performing a step of cooling the substrate to which the colored photosensitive resin layer is bonded after the step (1) in the present invention to prevent the generation of bubbles will be described in detail. Taking a PET film as an example of a base film, the PET film has a photosensitive layer of 10 mm under ordinary laminating conditions in the explanation of the operation principle (a).
Adhere to 0% substrate glass. PET by roll pressure
Transforms. Deformation consists of elastic deformation and plastic (creep) deformation. Elastic deformation consists of two components, a dynamic elastic force that recovers immediately and a relaxed elastic force that recovers gradually.

(B) After the roll pressure is released, the PET contracts and deforms due to the dynamic elastic deformation that recovers immediately. The photosensitive layer comes off the PET and adheres to the glass. At this time, the contracted and deformed P
A space appears between the ET and the photosensitive layer. When this space is generated, the photosensitive layer receives an external force and is simultaneously deformed. Since the deformation is not uniform and the photosensitive layer melts and flows easily due to the high temperature, bubbles are generated. In order to stop the generation of bubbles, the melt flow may be stopped by cooling the substrate. (C) After the roll pressure is released, the PET contracts and deforms due to the relaxation elastic deformation that gradually recovers. As time passes, the PET shrinks and the deformation (peeling of the PET) increases. At this time, the photosensitive layer is easily melted and flowable due to the high temperature.
Bubbles are generated. P shrunk and deformed over time
The space between the ET and the photosensitive layer becomes larger and bubbles are more likely to be generated. Therefore, in order to stop the generation of bubbles, the melt flow may be stopped by cooling the substrate.

Next, a cooling method in the step of cooling the substrate to prevent generation of bubbles will be described in detail. From the viewpoint of cooling in a short time, it is an excellent method to make contact with a cold plate. In addition, it is preferable to place a cooled plate or block having a high heat capacity and a large heat capacity at the exit of the laminating roll to perform rapid cooling of the substrate. The surface temperature of the plate or block is preferably room temperature or lower. Passing through cold water is also a good method. The temperature of the cold water is preferably room temperature or lower, and cold water with ice floating is most efficient. The blowing of cold air also has a good effect. It is also good to put on ice and cool. The method of rubbing by shaving ice in a container and smashing it onto the substrate immediately becomes cold, and the substrate temperature is 5
C to 7C.

The cooling is preferably performed within 20 seconds after the laminating step, more preferably within 5 seconds, particularly preferably within 3 seconds, and most preferably immediately after. . Further, the cooling temperature is preferably set to Tg or lower or softening point or lower of the bay film. If PET is used as the base film, 8
The temperature is preferably set to 0 ° C. or lower. Usually, the cooling temperature is-
The temperature is 195 to 60C, preferably -78 to 45C, more preferably -10 to 30C.

In the bonding step, it is preferable to use the transparent substrate by heating it from the viewpoint of adhesion, followability and the like. The heating temperature at this time is preferably 30 to 100 ° C. If the heating temperature is lower than 30 ° C., the followability tends to be poor, and if it exceeds 100 ° C., the adhesion tends to be poor. Further, the heating time is preferably set to 1 to 30 minutes. If the heating time is less than 1 minute, the adhesiveness and followability tend to be inferior, and if it exceeds 30 minutes, the workability tends to be inferior.

The feed speed at the time of bonding is 0.1 to 15
m / min. This feed rate is 0.1
If it is less than m / min, the workability tends to be poor, and
If it exceeds / minute, the adhesiveness and the followability tend to be inferior.
The roll pressure at the time of bonding is preferably 1 to 10 kgf / cm ² . If the roll pressure is less than 1 kgf / cm ² , the adhesiveness and followability tend to be poor, and
^If it exceeds ² , the preceding pixel tends to be deformed. Also,
The roll temperature at the time of bonding is preferably set to 80 to 140 ° C. When the roll temperature is less than 40 ° C., the adhesiveness and followability tend to be inferior. When the roll temperature is more than 140 ° C., depending on the material, white smoke may be emitted from the roll, and the photosensitive film tends to emit smoke. is there. In addition, a thermal reaction starts inside the photosensitive layer, cross-linking proceeds, and an unexposed portion remains even after development.

Preferably, the bonding step is performed under reduced pressure as bonding for forming a space between pixels, and the heating and / or pressurizing in the transition step is performed under reduced pressure.
By doing so, steps and poor followability are further improved. The means for reducing the pressure is not particularly limited, but usually a vacuum laminator is used. An example of a vacuum laminator is VACUUM LAMINATOR TYPE VCL manufactured by ANGER ELECTRONIC GMBH. The pressure at the time of pressure reduction is preferably 10 mmHg or less from the viewpoint of adhesiveness and the like. If this pressure exceeds 10 mmHg, the adhesiveness and followability tend to be poor.

The bonding is preferably performed in a wet state. For example, the bonding can be performed by processing the substrate and / or the colored photosensitive resin layer of the second color or later with water and then bonding. . That is, by softening the colored photosensitive resin layer by undercoating the photosensitive resin layer with water at the time of lamination, it is possible to improve the followability to unevenness, and when peeling the base film, there is a disadvantage that the protective film is peeled off together with the protective film. Thus, a fine pattern having a uniform thickness can be formed on a substrate with good workability, and a multicolor fine pattern having high accuracy and high heat resistance can be formed.

The bonding step may be a bonding step for forming a space between pixels, and the bonding may be performed after treating the substrate and / or the colored photosensitive resin layer of the second and subsequent colors with water. For example, by priming the photosensitive resin layer with water at the time of lamination and softening the colored photosensitive resin layer, when peeling off the base film, the disadvantage of peeling off together with the protective film is eliminated, and workability is good and uniform on the substrate. A fine pattern having an appropriate thickness can be formed, a multicolor fine pattern can be formed with high precision, and a color filter having excellent heat resistance can be manufactured.

The photosensitive film used in the present invention is a transparent base film, for example, by coating a photosensitive resin composition colored in one color on a film of polyethylene terephthalate, polyethylene, polypropylene or the like, and drying. This is one in which a colored photosensitive resin layer is formed. It is preferable to use a polyethylene terephthalate film as the base film from the viewpoint of applicability and the like. Since the photosensitive resin layer is flexible and has adhesiveness, it is preferable that a protective film such as a polyethylene film is further laminated on the photosensitive resin layer to prevent external damage, adhesion of foreign matter, and the like. The colored photosensitive resin layer formed on the photosensitive film, when having a protective film, is adhered to a transparent substrate while peeling off the protective film, and the base film on the surface of the colored photosensitive resin layer is removed after being exposed to a predetermined pattern. Is done.

The color filter according to the present invention is manufactured, for example, as follows. First, a colored photosensitive resin layer formed on a photosensitive film is laminated on a transparent substrate, and is exposed in a pattern by, for example, placing a negative mask of a predetermined pattern on a base film on the surface of the colored photosensitive resin layer and exposing the film. After that, the base film is removed, and in the case of a negative photosensitive resin layer, an unexposed portion is removed and developed with a developing solution, and in the case of a positive photosensitive resin layer, the exposed portion is removed with a developing solution. To develop a colored pattern (pixel). This colored pattern forming step is repeated a predetermined number of times using photosensitive films of different colors,
A color filter is obtained by forming a multicolor pattern. The peeling of the base film is performed after the exposure step and before the development step or before the exposure step. The color order of pixel creation is red,
In addition to the order of green, blue and black, black, blue, green and red, black,
Any color sequence is possible with the present invention, such as red, blue and green.

When a fine line is formed with the colored photosensitive resin layer adhered on the transparent substrate, the colored layer after development may be flexible because the exposure is performed with the minimum exposure amount that can withstand the developing solution. It is preferable that the colored layer is completely cured by irradiation with ultraviolet light, heat treatment or electron beam later to impart strength and heat resistance.

The colored photosensitive resin composition contains an ethylenically unsaturated compound (a), a carboxyl group-containing film imparting polymer (b), a photopolymerization initiator (c), and a pigment or dye (d). It is preferable that the thickness of the colored photosensitive resin layer of the photosensitive film produced by applying and drying this on a base film is 0.5 to 15 μm. The thickness of the colored photosensitive resin layer is 0.5 μm
If it is less than 15, the photocurability and chromaticity tend to be inferior.
If it exceeds μm, a step tends to occur. The thickness of the base film is usually 3 to 50 μm.

An intermediate layer can be provided between the base film and the colored photosensitive resin layer. The intermediate layer peels off from the base film and adheres to the colored photosensitive resin layer.The intermediate layer peels off from the colored photosensitive resin layer and does not peel off between the transparent substrate and the colored photosensitive resin layer. Required for properties. Although a material having an oxygen-blocking property is desirable, in the present invention, the exposure may be performed before the base film is peeled off, in which case the oxygen-blocking property is not necessary. In order to remove the intermediate layer at the same time when the colored photosensitive resin layer is developed, a material soluble in a developer can be used for the intermediate layer. However, an intermediate layer material that is insoluble in the developer can be used, in which case the intermediate layer must be removed before the development step. The thickness of the intermediate layer is 1-5μ
m, more preferably 2.0 to 4 μm. If it is less than 1 μm, the film strength tends to be inferior, and if it exceeds 5 μm, the resolution tends to be inferior.

Examples of the material of the intermediate layer include vinyl alcohol, an alkyl ester copolymer of vinyl acetate / acrylic acid, a polyvinyl ether / maleic anhydride copolymer, a water-soluble cellulose ether, and a combination of polyvinyl alcohol and polyvinyl pyrrolidone. And the like.

As the ethylenically unsaturated compound (a),
For example, compounds obtained by adding an α, β-unsaturated carboxylic acid to a polyhydric alcohol (trimethylolpropane diacrylate, trimethylolpropane triacrylate, tetramethylolmethane triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate) Acrylate), compounds obtained by adding an α, β-unsaturated carboxylic acid to a glycidyl group-containing compound (trimethylolpropane triglycidyl ether triacrylate, bisphenol A diglycidyl ether diacrylate, etc.), polyvalent carboxylic acid (anhydride) Esterified product of a compound having a hydroxyl group and an ethylenically unsaturated group (such as β-hydroxyethyl acrylate), an alkyl ester of acrylic acid (methyl acrylate, ethyl acrylate, Butyl acrylate, 2-ethylhexyl acrylate, etc.), urethane diacrylate compounds obtained by reacting trimethylhexamethylene diisocyanate, dihydric alcohol and dihydric acrylate monoester, and methacrylates corresponding thereto. Can be These compounds are used alone or in combination of two or more. In terms of light sensitivity and developability,
The amount of the component (a) is preferably 90 to 50 parts by weight based on 100 parts by weight of the total amount of the components (a) and (b).

Examples of the carboxyl group-containing film imparting polymer (b) include copolymers of alkyl acrylate or alkyl methacrylate with acrylic acid or methacrylic acid, alkyl acrylate or alkyl methacrylate and acrylic methacrylate. Copolymers of an acid or methacrylic acid with a vinyl monomer copolymerizable therewith are exemplified.

Examples of the alkyl acrylate include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and the like. Examples of the alkyl methacrylate include those corresponding to the above-mentioned alkyl acrylate. Examples of the copolymerizable vinyl monomer include, for example,
Dimethylaminoethyl acrylate, tetrahydrofurfuryl acrylate, aminoethyl acrylate, 2,2,2-trifluoroethyl acrylate,
2,2,3,3-tetrafluoropropyl acrylate, methacrylate, acrylamide, methacrylamide diacetone acrylamide, styrene, vinyltoluene and the like corresponding thereto.

(B) As the carboxyl group-containing film imparting polymer, for example, polyesters using terephthalic acid, isophthalic acid, sebacic acid, etc., copolymers of butadiene and acrylonitrile, cellulose acetate, cellulose acetate butyrate, methyl cellulose, Ethyl cellulose and the like can also be used in combination.
The use of the component (b) improves the coating properties and the film properties of the cured product, and the compounding amount is preferably from 10 to 50 parts by weight based on 100 parts by weight of the total amount of the components (a) and (b). . When the amount is less than 10 parts by weight, the photosensitivity tends to decrease due to an increase in the amount of the ethylenically unsaturated compound.
If the amount exceeds the weight part, the photocured product tends to become brittle. Further, the weight average molecular weight of the component (b) is preferably from 10,000 to 500,000 from the viewpoint of the coating properties and the film strength. The weight average molecular weight is a value converted into polystyrene by gel permeation chromatography.

Examples of the photopolymerization initiator (c) include aromatic ketones (benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), 4-methoxy-4'-dimethyl Aminobenzophenone, 4,4'-diethylaminobenzophenone, 2-
Ethyl anthraquinone, phenanthrene quinone, etc.), benzoin ether (benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, etc.), benzoin (methyl benzoin, ethyl benzoin, etc.), 2,4,5-triarylimidazole dimer, 2- (O-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl)-
4,5-di (m-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2-
(O-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5
-Diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer,
2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazole dimer, etc., acridine derivative (1,7- Bis (9-acridinyl) heptane and the like are used. These compounds are used alone or in combination of two or more.

The amount of the component (c) is 0.1 to 10 parts by weight based on 100 parts by weight of the total of the components (a) and (b).
Parts by weight are preferred. When the amount is less than 0.1 part by weight, the photosensitivity tends to be insufficient. When the amount exceeds 10 parts by weight, light absorption on the surface of the composition during exposure increases,
Light curing inside tends to be insufficient.

As the pigment or dye (d), generally known coloring agents can be used, and the compatibility with a photosensitive resin layer, particularly an ethylenically unsaturated compound or a carboxyl group-containing film-imparting polymer, is targeted. The selection is made in consideration of hue, light transmittance, and the like. As a pigment that can be used for a color filter, various compounds can be used.
Examples include inorganic pigments such as barium sulfate, zinc oxide, lead sulfate, titanium oxide, red iron oxide, carbon black, graphite, and chromium oxide, and the following organic pigments (color index numbers).

Yellow pigment: CI Pigment Yellow 20,
24, 83, 86, 93, 109, 110, 117, 1
25, 137, 138, 139, 147, 148, 15
3, 154, 166, 168 Orange pigment: CI Pigment Orange 36, 43, 5
1, 55, 59, 61 Red pigment: CI Pigment Red 9, 97, 122, 1
23, 149, 168, 177, 180, 092, 21
5, 216, 217, 220, 223, 224, 22
6, 227, 228, 240, 48: 1 Violet pigment: CI Pigment Violet 19,
23, 29, 30, 37, 40, 50 Blue pigment: CI Pigment Blue 15, 15: 6, 2,
2, 60, 64 Green pigment: CI Pigment Green 7, 36 Black pigment: CI Pigment Black 7

The amount of the component (d) is preferably 1 to 50 parts by weight based on 100 parts by weight of the total of the components (a) and (b). If the amount is less than 1 part by weight, the coloring tends to be insufficient, and if it exceeds 50 parts by weight, the light transmittance tends to decrease.

The colored photosensitive resin layer contains a melamine resin and / or an epoxy resin thermally reacting with a carboxyl group of a carboxyl group-containing film-imparting polymer in order to enhance the heat-curing property. Total amount of ingredients 10
It is preferable to add 1 to 20 parts by weight to 0 parts by weight and heat the mixture. The heating temperature is preferably from 130 to 200 ° C., and the heating time is preferably from 30 to 60 minutes, from the viewpoint of improving the crosslinking density of the colored layer, improving the heat resistance, and the like.

[0036]

The present invention will be described below by way of examples. Example 1 (1) Production of Coating Liquid for Colored Photosensitive Resin Layer 135 parts by weight of any of the pigment pastes of Table 2 and 200 parts by weight of a solution in which the materials of Table 1 were uniformly dissolved, and melamine resin 5
Parts by weight and 0.1 part by weight of a silane coupling agent were added and dissolved and dispersed to obtain a coating solution for a colored photosensitive resin layer.

[0037]

[Table 1]

[0038]

[Table 2]

Melamine resin Cymel 300 (trade name of hexamethoxymethyl melamine, manufactured by Mitsui Toatsu Chemicals, Inc.) Silane coupling agent KBM503 (manufactured by Shin-Etsu Chemical Co., Ltd.) Preparation of coating solution Immediately before, the dispersion was adjusted by ultrasonic waves for 2.5 hours.

(2) Production of photosensitive film The obtained coating solution of the colored photosensitive resin layer was microgravure to a uniform thickness on a 6 μm-thick polyethylene terephthalate film (Tetron film M5R manufactured by Teijin Limited). The coating was performed using a kiss touch reverse type coating machine loaded with a roll, and the coating was dried with a dryer at 100 ° C. for 1 minute. A 30 μm-thick polyethylene film was laminated as a protective film to obtain a photosensitive film. The thickness of the photosensitive resin layer after drying was 2.0 μm for all of red, blue and green.

(3) Production of Color Filter (a) Substrate Heating Step An undersubstrate for a color filter (a glass substrate having a thickness of 1.1 mm; a product name of Corning 7054, manufactured by Corning Incorporated) was prepared using 8
Heat at 0 ° C. for 10 minutes. (B) Laminating Step While peeling off the protective film of the color film photosensitive film, the colored photosensitive resin layer was laminated on the color filter base substrate under the following conditions. Roll temperature 120 ° C Roll pressure 6.0 kgf / cm ² Speed 0.5 m / min

(C) Step of cooling the substrate on which the colored photosensitive resin layer is bonded to prevent the generation of bubbles When forming pixels of the second and subsequent colors, the substrate is cooled immediately after lamination to prevent the generation of bubbles. It is. Immediately after the completion of lamination for the second and subsequent colors, the laminated substrate was immersed in cold water in which ice was floated (with a time delay of 1 second or less). Cold water temperature is 4 ℃
The temperature of the quenched laminate substrate measured by pulling up after 5 seconds was 4 ° C. (D) Exposure step A predetermined pattern (8 in a normal stripe pattern)
Exposure machine HMW-201 through a negative mask of 0 μm (white) / 220 μm (black) and 150 mm in length)
B (3 kW, ultra high pressure mercury lamp, manufactured by Oak Manufacturing Co., Ltd.). The quenched laminate substrate was exposed when the temperature was 14 ° C.

(E) Peeling Step The polyethylene terephthalate film was removed at room temperature. The film was peeled off with an automatic peeling device (prototype made in-house, a device for peeling polyethylene terephthalate film using a roll with double-sided tape attached). (F) Development Step Undeveloped portions were removed by spray development with a 0.08% by weight aqueous solution of Na ₂ CO ₃ at 30 ° C. for 15 seconds, washed with water after development, and dried by heating in an oven to form a colored pattern. (G) Exposed part curing step Irradiation was performed at 3 J / cm ² using an ultraviolet irradiator (lamp H5600L / 2, manufactured by Toshiba Electric Materials Co., Ltd.). Thermal curing was performed at 150 ° C. for 40 minutes.

The steps (a) to (g) of forming a colored pattern were repeated in the order of red, blue and green using photosensitive films of respective colors. At the time of lamination of the second color blue, the film was fed in a direction parallel to the red stripe pattern of the preceding pixel. The same applies to the third color, green, to form a multicolor pattern. The exposure amount at this time is 50 mJ / cm ² for the red, blue and green photosensitive resin layers.
And 3 J / cm ² was applied to the obtained multicolor pattern using an ultraviolet irradiator (lamp H5600L / 2, manufactured by Toshiba Denshi Co., Ltd.).
And heated at 150 ° C. for 45 minutes to obtain a color filter. The obtained color filter had red, blue and green patterns (striped patterns) arranged in order, had good followability, and was excellent without bubbles. Also, the step of the pixel is 0.12 μm for blue and 0.1 for green.
It was 15 μm. In the cross section of the pixel, it was recognized that green was M-shaped and blue was J-shaped.

Example 2 (b) The step of cooling the substrate to which the colored photosensitive resin layer was bonded to prevent the generation of bubbles was as follows.
The same procedures as in Example 1 were carried out except that the materials shown in Table 3 were used, and the same results as in Example 1 were obtained. (B) a step of cooling the substrate on which the colored photosensitive resin layer is bonded to prevent bubbles from being generated; when forming pixels of the second and third colors, at the time of forming pixels of the second and subsequent colors, immediately after lamination, Was cooled to prevent the formation of air bubbles. Immediately after lamination of the second and subsequent colors, the laminate substrate was brought into contact with a cold iron plate at room temperature immediately (with a time delay of 1 second or less). The temperature of the cold iron plate was 21 ° C., and after 65 seconds, the temperature was raised and measured. The temperature of the quenched laminate substrate is 21
° C.

[0046]

[Table 3]

Example 3 (b) The step of cooling the substrate to which the colored photosensitive resin layer is bonded to prevent the generation of bubbles is as follows.
The same operation as in Example 1 was performed except that the materials in Table 4 below were replaced with the materials in Table 1, and the same results as in Example 1 were obtained. (B) a step of cooling the substrate to which the colored photosensitive resin layer is bonded to prevent the generation of bubbles; immediately after lamination when forming the second and third color pixels, immediately after lamination when forming the second and subsequent pixels. The substrate was cooled to prevent the generation of air bubbles. Immediately after the completion of lamination for the second and subsequent colors, dry air at a room temperature of 22 ° C. was blown for 20 seconds (with a time delay of 1 second or less). The temperature of the quenched laminate substrate measured after spraying was 22 ° C.

[0048]

[Table 4]

Comparative Example 1 A color filter was manufactured in the same manner as in Example 1 except that the step of (b) cooling the substrate on which the colored photosensitive resin layer was bonded and preventing the generation of bubbles was omitted. Created. That is, natural cooling is left to natural cooling. The step of forming a colored pattern was repeatedly performed in the order of red, blue, and green using the photosensitive film of each color. At the time of lamination of the second color blue, the film was fed in a direction parallel to the red stripe pattern of the preceding pixel. The same applies to the third color, green, to form a multicolor pattern. The exposure amount at this time is 5 for the red, blue and green photosensitive resin layers.
It was set to 0 mJ / cm ² . The obtained multicolor pattern was subjected to UV irradiation using a UV irradiator (Lamp H5600L / 2, manufactured by Toshiba Electric Materials Co., Ltd.)
After irradiation at J / cm ² , the mixture was heated at 150 ° C. for 45 minutes to obtain a color filter. The obtained color filter had red, blue, and green patterns (striped patterns) arranged neatly. However, many bubbles were generated, and many white spots were observed in green and blue. As a color filter, many air bubbles were generated and could not be put into practical use.

[0050]

According to the method for manufacturing a color filter according to the first aspect of the present invention, a color filter having excellent heat resistance and having a multi-color fine pattern with no air bubbles and small steps between pixels can be manufactured. Can be.

Claims (1)

[Claims] 1. A step of laminating a photosensitive film having a base film and a colored photosensitive resin layer on a transparent substrate such that the colored photosensitive resin layer faces the substrate, 2) In a method for manufacturing a color filter in which a multicolor pattern is formed by repeating an exposure step of exposing in a pattern and (3) a step including a development step, in a step of a second color or later, a color is formed after the step of (1). A process for cooling the substrate to which the photosensitive resin layer is adhered to prevent generation of bubbles.